Aldimine salts of petroleum sulphonic acids



- Patented Mar. 3 1, 1942 ALDIMINE SALTS F PETROLEUM SULPHONIC aoms Melvin De Groote, University City, Mo., assignor, by mesne assignments, to Petrolite Corporation, Ltd., a corporation of Delaware No Drawing. Application May 12, 1939,

Serial No. 273,222

2 Claims.

This invention relates to a new composition of matter consisting of a certain kind of amine salt derived from water-soluble petroleum sulphonic acid or acids of the kind hereinafter de-' scribed.

The object of my invention is to provide a new material or composition of matter that is an eflicient solubilizer, particularly in instances where it is desired to make two immiscible materials mutually soluble, and whichis also capable of use as a demulsifier for crude oil emulsions, either alone or in admixture 'with conventional demulsifying agents, such, for example, as-demulsifying agentsof the modified fatty acid type, or of the alkylated aromatic sulphonic acid type.

Petroleum sulphohic acids are produced from a wide variety of petroleum distillates or petroleum fractions, and in some instances, they are produced from the crude petroleum itself. When produced from crude petroleum itself, it is customary to use crude oil of the naphthene type, crude oil of the paraflln type, crude oil of the asphaltic type, and mixtures of said three different types of crude oil. v

The art of refining petroleum crude or various fractions, using sulphuric acid of various strengths, as well as monohydrate and fuming acid, is a well known procedure. In such conventional refining procedure, petroleum sulphonic acids have been produced as by-products. For instance, in removing the olefinic components, it has been common practice to use sulphuric acid, so as to polymerize the olefines or convert them into sulphonic acids, which are subsequently removed. Likewise, in the production of white oil or highly refined lubricating oils, it has been customary to treat with fuming sulphuric acid,

so as to eliminate certain undesirable components.

In recent years, certain mineral oil fractions have been treated with sulphuric acid with the primary object of producing petroleum sulphonic acids, and in such procedure the petroleum sulphonic acids represented the primary objects of reaction, rather than concomitant by-products.

Petroleum sulphonic acid,regardless of whether derived as the principal product of-r'eaction or as a by-product, can be divided into two general types, to wit, green acid or acids and mahogany acid or acids. The green acids are characterized by being water-soluble or dispersible. In other words, they form either true solutions or sols. For purpose of convenience, they will be herein pearance.

colloidal 'in nature. The green acids, as indicated by their name, frequently give an aqueous solution having a dark green or grey-green ap- They generally appear as a component of the acid draw-off, and'do not remain behind dissolved in the oil fraction which has been subjected to sulphuric acid treatmen The green acids arenotsoluble in oil, even Whig! substantially anhydrous, and certainly are no soluble in oil when they contain as much as of water. Similarly, their salts obtained by neutralization with a strong solution of caustic soda.

caustic potash, or ammonia, are not oil soluble.

- For convenience of classification, the ammonium if they contain some dissolved water. Some of the mahogany acids also show limited hydro philic properties to the extent that either some water can be dissolved in the acids, or they, in turn, may dissolve to some extent in water. In some instances their salts, such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol. However, regardless of the presence of any hydrophilic properties whatsoever, they always have a characteristic hydrophobe property, as indicated by the fact that the substantially anhydrous form, for instance, their' alkali salts containing 5-12% water, will dissolve in oil. This clearly distinguishes them from the green acids previously referred to,

because the green acids in similar form containing the same amountof water, for example, will 1 not dissolve in oil. The green acids, assuch, are

essentially hydrophilic and non-hydrophobic in character. v

The utility of the mahogany acids in various arts has been enhanced by increasing their water solubility; for instance, converting the mahogany othe acids to hydroxy alkylamine salts.

pro uct of commerce has resulted from decreasing the water solubility of the mahogany acids by the addition of some oil-soluble basic amine,

completely devoid of any solubility in water which the alkali salts may have exhibited and show,

i referred to 'as water-soluble, without any efiort to indicate whether the solution is molecular or hydrophobe solvents.

as would be expected, an increased solubility in On the' and, as "far as 'I am aware, no valuable Green acids are hydrophile in character, as previously-stated. Their hydrophile character has been increased by neutralization with material such as trlethanolamine and the like. Such green acid salts having enhanced water solubility as compared with the ordinary alkali salts,

, have found application in certain arts.

I have found that when green acids, i. e., the oil-insoluble type, are neutralized with a substituted aldimine, as hereinafter described, so as.

to produce a water-insoluble product that the,

resulting materiaheven though it does not exhibit any marked oil solubility, especially when it contains 5-10% of water, still has pronounced value as a demulsifier for oil field emulsions, eitherwhen used alone, or in conjunction with other known demulsifying agents. I employ a substituted aldimine of the kind derivable most readily by reactions involving an aldehyde and an amine other than an arylamine. Details as to the manufacture and nature of such bases are hereinafter described. I have also found that such substituted aldimine salts of green acids will mix in with a hydrophobe material and a hydrophile material, so as to produce a homogeneous mixture. The effectiveness of the above described material or composition of matter as a demulsifying agent for oil field emulsions apPQars to be related to some factors other than its solubility characteristics.

The new composition of matter which constitutes my present invention is represented by substituted aldimine salts of hydrophilic, nonhydrophobic green .petroleum acids, as exemplified by the salt derived from such green acids 7 petroleum acid with one molecule of a suitable by neutralization with a base obtained by, reaction between a mole of octylamine and a 'mole of acetaldehyde. The manufacture of said composition of-matter involves nothing more or less than neutralizing one molecule of the selected base until neutral to methyl orange indicator other suitable indicators. For purposes of c nvenience, I prefer that the selected petroleum sulphonic acid contain not over of water.-

It is understood, of course, that the conventional procedure in employing double decomposition, instead of direct neutralization can be utilized in the' manufacture of my new material or composition of matter. For instance, the sodium salt of the selected petroleum sulphonic acid can be dissolved in alcohol or other suitable solvent,

and'the base hydrochloride added so that sodium chloride will precipitate; After filtering off the precipitated sodium chloride, thealcohol can be aldehyde and aniline.

If an aldehyde, for instance, acetaldehyde, is converted into the imide, i. e., the aldo-imide, sometimes known as the aldo-imine, or aldimine, then the transformation may be indicated in the aniline react to form ethylidine following manner:

and in the case of a Schifls base, or an anil, the-- composition is similar, except that T represents an aryl residue, Obviously, one need not depend on reactions involving formaldehyde, for instance,

or acetaldehyde; but one may employ aldehydes of higher molecular weight, such as heptaldehyde, octaldehyde, lauric aldehyde, palmitic aldehyde, hexahydro-benzaldehyde; phenyl-acetaldehyde, and stearic aldehyde, etc. As a matter of fact, when afldehydes of low molecular weight are employed, there is a greater tendency to obtain reactions other than the desired substituted aldimine. .Note, for instance, the following statement found in Richters Organic Chemistry, Allott,-volume 1, third (1934) .edition, page 250:

By the use of aldehydes of higher molecularweight, the tendency to polymerization on the partof the reaction products of primary amines and aldehydes diminishes and Schiffs bases are formed. I

evaporated and the petroleum sulphonic-acid salt recovered. v.1

It so happens that the commonest example of a substituted aldimine represents a type of material not employed in the present instance. Reference is made to the type of material frequently known as a Schiifs base, andsometimes,

in order to emphasize its aromatic character as an anil. Such materials are obtained by reactions between an arylamine and an aldehyde, which may or may not be aromatic-in nature.

Methylisobutylideneamine (CH3)aCI-I.CH=N.CH3, B. P. 68.

NoTE.-In this instance the term "Schiffs base is not limited to'aromatic materials such as nails, but is extended to non-aryl compounds.

Commercially, heptaldehyde is most readily available, in view of its manufacture, by the distillation of'castor 011. My preference is to react heptaldehyde with octylamine, so as to obtain the corresponding octyl aldimine.

.In,the manufacture of such compounds, any suitable non-aryl primary amine can be employed, but I have found, by experience, that generally speaking, it is most desirable to use the most readily available amine, such as monoamylamine, monocyclohexylamine, benzylamine, or octylamine. Amines of higher molecular weight, such as oleylamine, may be employed.

- Instead of cyclohexylamine, one may, of course,

Reference is made to the following statement,

which is found in Textbook of Organic Chemise try, by Richter, 1938, page 502 The reaction. of primary aryl amines and aldehydes leads toa type compound referred to as a Schifls base or .azomethine, substances which contain the structure CH=N--. Acetemploy homologues obtained by the hydrogenation of methyl aniline or the like, instead of by Similarly, benzylamine may 'be looked upon as a derivative of the hydrogenation of aniline.

benzyl alcohol, and one may accordingly use other homologues derived from homologues of benzyl alcohol. A wide variety of alkylamines,

of course, are available; and those employed may contain a hydroxy radical, such as monobutanolamine, monopentanolamine, monoethanolamine,

hydroxyether amine (OHC2H4OC2H4NH2) and the like. My preference, however, is to use noncarcass hydronvlated nonaryl amines. Hexadecylamine and octadecylamine may be employed. An aromatic aldehyde, such as benzaldehyde, may be employed; unsaturated aldehydes, such as acrolein, crotonaldehyde, or tiglic aldehyde, may be employed, but are objectionable, due to the fact that they enter into an entirely different series of reactions with primary amines. Heterocyclic aldehydes, such as furfuraldehyde, may be employed. Similarly, one may employ hydroxy aldehydes, such as aldol; but here again, the use of such a substituted aldehyde is objectionable, in that another series of undesirable reactions may take place. My preference is to employ an unsubstituted aldehyde having at least five car bon atoms and not more than 8 carbon atoms, such as furfural, benzaldehyde, or heptaldehyde, and further characterized by freedom from an unsaturated aliphatic group. One may also employ an aralkyl aldehyde, such as phenylacetaldehyde, CcH5.CH2.CI-IO, or an alicyclic aldehyde, such as hexahydro-berizaldehyde.

If an aldehyde is employed in which an alcoholic hydroxyl radical is present, then either prior to or after the formation of the aldimine, the hydroxyl radical may be removed, if desired,

by an acylation reaction involving a member of the lower fattyacid series, such as acetic acid, butyric acid, heptoic acid, or the like, having seven carbon atoms or less; or by an acid having at least 8 carbon atoms and not more than 32 carbon atoms, and of the kind referred to as a detergent-forming acid, such as a fatty acid, in-

cluding oleic acid, stearic acid, and the like; or a petroleum acid, such as a naphthemc acid, or a resin acid, such as abietic acid. In such acylation reactions, instead of employing the acid, one may employ any suitable compound, such as the acyl chloride, anhydride, etc. Similarly, one may acylate the hydroxyl radical or radicals attached to an amine, as in the case of ethanolamine or glycerylarnine. In such acylation reactions, precautions must be taken to prevent any undesirable side" reactions; as, for instance, if monopropanolamine is esterified with an acid, the formation of a substituted amide or an imide must be prevented. Similar dificulties may arise in the acylation of a materialsuch as aldol, as, for example, a condensation of the type commonly known as an aldol condensation. For this reason, in most instances, if it is deemed undesirable to remove an alcoholiform hydroxyl from the substituted aldimine, such hydrowl should be removed after the substituted aldiinine has been formed.

The substituted aldimine employed in the present process may be characterized by the formula:

in which B is a hydrogen atom or a residue derived from analdehyde and may be alkyl, sralkyl, aryl alicyclic, or heterocyclic in nature; and T is a residue derived from a primary amine and may be alkyl, aralml, or alicyclic innature, or hydroxylated derivatives of these three types, or 'acylation compounds derived from acids or their functional equivalents, and such lrvdroxy hy drocarbon radicals.

My preferred reagent ismanui'actured in the manner which has already been suggested in considerable detail. Technically pure heptaldehyde derived from castor oil is cautiously reacted with octylamine, so as to produce the corresponding octyl aldimine; or, for the sake of convenience, will be indicated as octyl heptaldimine.

The reaction takes place very readily at ordinary temperature, and sometimes must be retarded by means of a cooling agency during the early stages of the reaction. During the latter stages of the reaction, moderate heat may be employed to insure completion. If desired, conventional procedures may be employed to'eliminate unreacted aldehyde or unreacted amine. However, if the reaction is conducted carefully, a

substantial and generous yield of the desired aldimine is obtained, and it is unnecessary to resort to any purification. It has been previously pointed out that having obtained an amine of the kind: desired, it is only necessary to proceed to neutralize the green acid, as previously indicated.

Obviously, as to the preparation of the preferred reagent, no additional information is required. However, it may be well to point out that I I prefer to use a green acid selected so that it is relatively free from inorganic acids, such as sulphurous acid and sulphuric acid, and containing not over 15 water, and preferably as little unsulphonated hydrocarbon material as possible. A

convenient amount of such material, for instance, a thousand pounds, is neutralized with octyl heptaldamine previously described, so that the resultant compound indicates neutral or slightly basic to methyl orange, or some other acceptable indicator. I

It may be well to point out that hydrophile nonhydropho'be petroleum sulphonic acid or acids of the green acid type vary somewhat; for instance, the molecular weightmay vary within the range of 350-500 or thereabouts. Naturally, these petroleum sulphonic acids may carry some polymerized olefines, free hydrocarbons, or the like, or may even carry a bit of naphthenic acids which represent carboxylated nonsulphonated petroleum acids. As previously stated, these materials are well known commercial products and are available in the'open market either in the form of ,the acid itself, or in the form of a salt.

in the claims the aldimine is referred to as basic, to indicate that the basicity is in the neighborhood or that or ammonia, triethanolamine, or amylamine. In some cases the basicity may be somewhat greater, in tact, perhaps considerably greater, and in some instances, slightly less. In order to insure such basicity, it is necessary that there be no aryl or aromatic radical attached to the amino nitrogen atom from which the substituted aldimine is produced. In other words, such materials as aniline, naphthylamine, etc, are not satisfactory, due tothe presence of an aryl radical attached indirectly to the amino nitrogen atom. The substituted aldimines derived from such aromatic bases result in the formation of Schifis bases, previously described,

which are of such low basicity that they do not form stable salts with the petroleum acids of the kind described. For this reason, th s expression basic is employed to clearly characterize the substituted aldimine. The term sulphonic acid used in the claims, is intended to refer to a substance consistlna either of a single acid or a mixture of acids. 7

In my divisional application Serial No. 300,- 844, filed Oct. 23, 1939, now Patent 2,226,122, I have described a novel process for resolving or breaking petroleum emulsions of the water-inoil type. said process involves subjecting the emulsion to the action of a demulsifier consisting oi the above described new material or composition oi matter. Said material is used either alone, or in admixture with another or with other conventional demulsifylng agents, and its method of use is the same as that generally employed in resolving or breaking petroleum emulsions oi the water-in-oil type with a chemical demulsifler. Briefly stated, the conventional method of usinga chemical demulsifler to break a petroleum emulsion consists in introducing the demulsifler into the well in which the emulsion is produced; introducing the demulsifier into a conduit through which the emulsion is flowing; or introducing the demulsifier into a tank in which the emulsion is stored. After treatment the emulsion is allowed to stand in a quiescent state, usually in a settling tank and usually at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough to prevent the volatilization of valuable constituents of the oil. The amount of demulsifier that may be required to break the emulsion may vary from 1 part of demulsifier to 500 parts of emulsion, up to 1 part of demulsifier to 20,000, or even 30,000 parts of emulsion. t

I desire to point out that the superiority of the reagent or demulsifying agent herein described is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsiiying agent has commercialivalue, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsiiying agents heretofore available.

Having thus described my invention, what I hydrocarbon radicals, alicyclic hydrocarbon radicals, aliphatic hydrocarbon radicals interrupted at least once by an oxygen atom, aliphaticallybound hydroxy hYdlOCfllOOIl radicals and hydroxy alicyclic radicals; said aldimine salt being obtained from water-soluble, non-hydrophobe petroleum sulphonic acid of the green acid type.

2. A new compound, consisting oi a water insoluble salt of a basic substituted aldimine of the formula type: 

